Composite particles and method for making the same

ABSTRACT

A composite particle is provided that comprises a base particle comprising at least a pigment or dye and cross-linked polyurea, a plurality of hydrophilic oligomeric groups, and a plurality of amine groups on the exterior portion of the base particle, and a steric stabilization polymer which is chemically bonded or physi-sorbed on the surface of the base particle. The cross-linked polyurea may form a network throughout the base particle. A method of making the composite particle includes providing either a solution containing a dye or a dispersion containing a pigment in a water-dispersible polyfunctional isocyanate dissolved in a water-miscible solvent, forming an emulsion of the solution/dispersion in water, agitating the emulsion while the polyfunctional isocyanate is converted into a cross-linked polyurea, and separating the composite particle containing the cross-linked polyurea and the dye/pigment from the emulsion.

REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.16/882,975 filed on May 26, 2020 (Publication No. 2020/0285127), whichis a continuation of U.S. patent application Ser. No. 15/947,027 filedon Apr. 6, 2018, (U.S. Patent Publication No. 2018/0267383; now U.S.Pat. No. 10,705,405), which claims priority to U.S. patent applicationSer. No. 15/463,328, filed on Mar. 20, 2017, now U.S. Pat. No. 9,995,987

FIELD OF THE INVENTION

This invention relates to composite particles used in electrophoreticdisplay media, as well as to the improved methods of manufacturing thecomposite particles.

BACKGROUND OF INVENTION

The term “electro-optic”, as applied to a material or a display, is usedherein in its conventional meaning in the imaging art to refer to amaterial having first and second display states differing in at leastone optical property, the material being changed from its first to itssecond display state by application of an electric field to thematerial. Although the optical property is typically color perceptibleto the human eye, it may be another optical property, such as opticaltransmission, reflectance, luminescence, or, in the case of displaysintended for machine reading, pseudo-color in the sense of a change inreflectance of electromagnetic wavelengths outside the visible range

Some electro-optic materials are solid in the sense that the materialshave solid external surfaces, although the materials may, and often do,have internal liquid- or gas-filled spaces. Such displays using solidelectro-optic materials may hereinafter for convenience be referred toas “solid electro-optic displays”. Thus, the term “solid electro-opticdisplays” includes rotating bichromal member displays, encapsulatedelectrophoretic displays, microcell electrophoretic displays andencapsulated liquid crystal displays.

The terms “bistable” and “bistability” are used herein in theirconventional meaning in the art to refer to displays comprising displayelements having first and second display states differing in at leastone optical property, such as black and white, and such that after anygiven element has been driven, by means of an addressing pulse of finiteduration, to assume either its first or second display state, after theaddressing pulse has terminated, that state will persist for at leastseveral times, for example at least four times, the minimum duration ofthe addressing pulse required to change the state of the displayelement. Some particle-based electrophoretic displays are stable notonly in their extreme black and white states but also in three or morestates, such as multi-color displays having three or more colors. Forconvenience the term “bistable” may be used herein to cover displayelements having two or more display states.

One type of electro-optic display, which has been the subject of intenseresearch and development for a number of years, is the particle-basedelectrophoretic display, in which a plurality of charged particles movethrough a fluid under the influence of an electric field.Electrophoretic displays can have attributes of good brightness andcontrast, wide viewing angles, state bistability, and low powerconsumption when compared with liquid crystal displays. Nevertheless,problems with the long-term image quality of these displays haveprevented their widespread usage. For example, particles that make upelectrophoretic displays tend to settle, resulting in inadequateservice-life for these displays.

Numerous patents and applications assigned to or in the names of theMassachusetts Institute of Technology (MIT), E Ink Corporation, E InkCalifornia, LLC and related companies describe various technologies usedin encapsulated and microcell electrophoretic and other electro-opticmedia. Encapsulated electrophoretic media comprise numerous smallcapsules, each of which itself comprises an internal phase containingelectrophoretically-mobile particles in a fluid medium, and a capsulewall surrounding the internal phase. Typically, the capsules arethemselves held within a polymeric binder to form a coherent layerpositioned between two electrodes. In a microcell electrophoreticdisplay, the charged particles and the fluid are not encapsulated withinmicrocapsules but instead are retained within a plurality of cavitiesformed within a carrier medium, typically a polymeric film. Thetechnologies described in these patents and applications include:

(a) Electrophoretic particles, fluids and fluid additives; see forexample U.S. Pat. Nos. 5,961,804; 6,017,584; 6,120,588; 6,120,839;6,262,706; 6,262,833; 6,300,932; 6,323,989; 6,377,387; 6,515,649;6,538,801; 6,580,545; 6,652,075; 6,693,620; 6,721,083; 6,727,881;6,822,782; 6,831,771; 6,870,661; 6,927,892; 6,956,690; 6,958,849;7,002,728; 7,038,655; 7,052,766; 7,110,162; 7,113,323; 7,141,688;7,142,351; 7,170,670; 7,180,649; 7,226,550; 7,230,750; 7,230,751;7,236,290; 7,247,379; 7,277,218; 7,286,279; 7,312,916; 7,375,875;7,382,514; 7,390,901; 7,411,720; 7,473,782; 7,532,388; 7,532,389;7,572,394; 7,576,904; 7,580,180; 7,679,814; 7,746,544; 7,767,112;7,848,006; 7,903,319; 7,951,938; 8,018,640; 8,115,729; 8,119,802;8,199,395; 8,257,614; 8,270,064; 8,305,341; 8,361,620; 8,363,306;8,390,918; 8,582,196; 8,593,718; 8,654,436; 8,902,491; 8,961,831;9,052,564; 9,114,663; 9,158,174; 9,341,915; 9,348,193; 9,361,836;9,366,935; 9,372,380; 9,382,427; and 9,423,666; and U.S. PatentApplications Publication Nos. 2003/0048522; 2003/0151029; 2003/0164480;2003/0169227; 2003/0197916; 2004/0030125; 2005/0012980; 2005/0136347;2006/0132896; 2006/0281924; 2007/0268567; 2009/0009852; 2009/0206499;2009/0225398; 2010/0148385; 2011/0217639; 2012/0049125; 2012/0112131;2013/0161565; 2013/0193385; 2013/0244149; 2014/0011913; 2014/0078024;2014/0078573; 2014/0078576; 2014/0078857; 2014/0104674; 2014/0231728;2014/0339481; 2014/0347718; 2015/0015932; 2015/0177589; 2015/0177590;2015/0185509; 2015/0218384; 2015/0241754; 2015/0248045; 2015/0301425;2015/0378236; 2016/0139483; and 2016/0170106;

(b) Capsules, binders and encapsulation processes; see for example U.S.Pat. Nos. 6,922,276 and 7,411,719;

(c) Microcell structures, wall materials, and methods of formingmicrocells; see for example U.S. Pat. Nos. 7,072,095 and 9,279,906;

(d) Methods for filling and sealing microcells; see for example U.S.Pat. Nos. 7,144,942 and 7,715,088;

(e) Films and sub-assemblies containing electro-optic materials; see forexample U.S. Pat. Nos. 6,982,178 and 7,839,564;

(f) Backplanes, adhesive layers and other auxiliary layers and methodsused in displays; see for example U.S. Pat. Nos. 7,116,318 and7,535,624;

(g) Color formation and color adjustment; see for example U.S. Pat. Nos.7,075,502 and 7,839,564;

(h) Methods for driving displays; see for example U.S. Pat. Nos.7,012,600 and 7,453,445;

(i) Applications of displays; see for example U.S. Pat. Nos. 7,312,784and 8,009,348; and

(j) Non-electrophoretic displays, as described in U.S. Pat. No.6,241,921 and U.S. Patent Applications Publication No. 2015/0277160; andapplications of encapsulation and microcell technology other thandisplays; see for example U.S. Patent Application Publications Nos.2015/0005720 and 2016/0012710.

Many of the aforementioned patents and applications recognize that thewalls surrounding the discrete microcapsules in an encapsulatedelectrophoretic medium could be replaced by a continuous phase, thusproducing a so-called polymer-dispersed electrophoretic display, inwhich the electrophoretic medium comprises a plurality of discretedroplets of an electrophoretic fluid and a continuous phase of apolymeric material, and that the discrete droplets of electrophoreticfluid within such a polymer-dispersed electrophoretic display may beregarded as capsules or microcapsules even though no discrete capsulemembrane is associated with each individual droplet; see for example,the aforementioned U.S. Pat. No. 6,866,760. Accordingly, for purposes ofthe present application, such polymer-dispersed electrophoretic mediaare regarded as sub-species of encapsulated electrophoretic media.

An electrophoretic display normally comprises a layer of electrophoreticmaterial and at least two other layers disposed on opposed sides of theelectrophoretic material, one of these two layers being an electrodelayer. In most such displays both the layers are electrode layers, andone or both of the electrode layers are patterned to define the pixelsof the display. For example, one electrode layer may be patterned intoelongate row electrodes and the other into elongate column electrodesrunning at right angles to the row electrodes, the pixels being definedby the intersections of the row and column electrodes. Alternatively,and more commonly, one electrode layer has the form of a singlecontinuous electrode and the other electrode layer is patterned into amatrix of pixel electrodes, each of which defines one pixel of thedisplay. In another type of electrophoretic display, which is intendedfor use with a stylus, print head or similar movable electrode separatefrom the display, only one of the layers adjacent the electrophoreticlayer comprises an electrode, the layer on the opposed side of theelectrophoretic layer typically being a protective layer intended toprevent the movable electrode damaging the electrophoretic layer.

An encapsulated electrophoretic display typically does not suffer fromthe clustering and settling failure mode of traditional electrophoreticdevices and provides further advantages, such as the ability to print orcoat the display on a wide variety of flexible and rigid substrates.(Use of the word “printing” is intended to include all forms of printingand coating, including, but without limitation: pre-metered coatingssuch as patch die coating, slot or extrusion coating, slide or cascadecoating, curtain coating; roll coating such as knife over roll coating,forward and reverse roll coating; gravure coating; dip coating; spraycoating; meniscus coating; spin coating; brush coating; air knifecoating; silk screen printing processes; electrostatic printingprocesses; thermal printing processes; ink jet printing processes;electrophoretic deposition (See U.S. Pat. No. 7,339,715); and othersimilar techniques.) Thus, the resulting display can be flexible.Further, because the display medium can be printed (using a variety ofmethods), the display itself can be made inexpensively.

In the design of electrophoretic displays, it is frequently necessary totailor the properties of electrokinetically mobile pigment particles tosatisfy multiple criteria, and it is not uncommon that the demands ofone criterion conflict with those of another. For example, it may berequired to provide an optically transparent colored pigment that isreadily switched by a dielectrophoretic mechanism. In order for such apigment to exhibit transparency, it must comprise particles small enoughnot to scatter visible light. However, in order to be switcheddielectrophoretically, a particle should ideally be large, so that afield gradient may induce a substantial dipole moment. One way tosatisfy both demands is to construct a composite particle in which smallpigment particles (required for transparency) are incorporated into alarge super-particle (that exhibits appropriate dielectrophoreticmobility). Thus, there is a need for efficient methods of incorporatingsmall pigment particles into large composites that can themselves befunctionalized appropriately for electrokinetic mobility.

SUMMARY OF THE INVENTION

According to one aspect of the present invention, a composite particleis provided that comprises, a base particle and a plurality ofhydrophilic oligomeric groups on an exterior portion of the baseparticle, the base particle including a cross-linked polyrurea and atleast one of a pigment and a dye. The cross-linked polyurea may form anetwork throughout the base particle.

According to another aspect of the present invention, a method of makinga composite particle is provided. The method comprises providing eithera solution containing a dye or a dispersion containing a pigment in awater-dispersible polyfunctional isocyanate dissolved in awater-miscible solvent, forming an emulsion of the solution/dispersionin water, agitating the emulsion while the polyfunctional isocyanate isconverted into a cross-linked polyurea, and separating the compositeparticle containing the cross-linked polyurea and the dye/pigment fromthe emulsion.

It is yet another aspect of the present invention to provide anelectrophoretic medium comprising a plurality of electrically chargedparticles disposed in a fluid and capable of moving through the fluidunder the influence of an electric field, wherein at least one of theparticles is produced by a process according to an embodiment of thepresent invention. The electrically charged particles and the fluid maybe confined within a plurality of capsules or microcells. Alternatively,the electrically charged particles and the fluid may be present as aplurality of discrete droplets surrounded by a continuous phasecomprising a polymeric material. The fluid may be liquid or gaseous. Theelectrophoretic material containing the electrophoretic medium may beincorporated into an electrophoretic display comprising a layer of theelectrophoretic material and at least one electrode arranged to apply anelectric field to the layer of electrophoretic material.

The displays incorporating the electrophoretic medium made according tothe various embodiments of the present invention may be used in anyapplication in which prior art electro-optic displays have been used.Thus, for example, the present displays may be used in electronic bookreaders, portable computers, tablet computers, cellular telephones,smart cards, signs, watches, shelf labels, variable transmission windowsand flash drives.

These and other aspects of the present invention will be apparent inview of the following description.

BRIEF DESCRIPTION OF THE FIGURES

The drawing Figures depict one or more implementations in accord withthe present concepts, by way of example only, not by way of limitations.In the figures, like reference numerals refer to the same or similarelements.

FIG. 1 is a schematic representation of a Prior Art method of forming amicrocapsule; and

FIG. 2 is a schematic representation of a method of forming a compositeparticle according to an embodiment of the present invention.

DETAILED DESCRIPTION

In the following detailed description, numerous specific details are setforth by way of examples in order to provide a thorough understanding ofthe relevant teachings. However, it should be apparent to those skilledin the art that the present teachings may be practiced without suchdetails.

The composite particles according to the various embodiments of thepresent invention comprise a cross-linked polyurea that forms a networkthroughout a base particle. As used herein in the specification and theclaims, forming “a network throughout a base particle” means that thecross-linked polyurea is present at multiple locations/radii within theentire thickness of the base particle. Therefore, excluded from thedefinition of “a network throughout a base particle” would be a polyureashell of a microcapsule because the shell is generally present onlyaround the outer periphery of the microcapsule, for example.

In one method according to an embodiment of the present invention, thecross-linked polyurea may be obtained from a water-dispersiblepolyfunctional isocyanate. On contact with water, the isocyanate groupof a polyfunctional isocyanate hydrolyzes, releasing carbon dioxide andforming an amine. Amino groups react more readily than water withisocyanates; therefore, the newly-formed amine is likely to react with aneighboring, unhydrolyzed isocyanate. This reaction produces a ureagroup, and thus the final result of the reaction is a cross-linkedpolyurea that also contains some free amino groups.

Water-dispersible polyfunctional isocyanates typically contain ahydrophilic oligomeric group (often an aliphatic oligomer, such aspoly(ethylene oxide)) and multiple isocyanate groups. The portion of themolecule that bears the isocyanate groups is essentially insoluble inwater. When the polyfunctional isocyanates are combined with animmiscible solvent and emulsified in a continuous aqueous phase, themixture of polyfunctional isocyanates and solvent form micelles, asillustrated in FIG. 1 , wherein the poly(ethylene oxide) units (11) ofthe polyfunctional isocyanates are solvated by water and stabilize thewater interface while the more hydrophobic interior of the micellecontains most of the isocyanate functionality (10). The isocyanategroups (10) may react as described above to form a polyurea shell (13)around the immiscible solvent (12) to form a microcapsule.

Without wishing to be bound by theory, it is believed that by firstdissolving the water-dispersible polyfunctional isocyanates in awater-miscible solvent, a composite particle may be formed having apolyurea network throughout a base particle of the composite. Referringto FIG. 2 , which is a schematic representation of an embodiment of theinvention, a mixture of a water-dispersible polyfunctional isocyanateand water-miscible solvent is introduced to water (with agitation), suchthat solvent droplets (14) stabilized at the aqueous interface by thehydrophilic oligomeric groups (11) will be formed. Diffusion of waterinto the solvent droplet (14) will cause the polyfunctional isocyanatesto polymerize by the hydrolysis reaction and amine condensationdescribed above, while diffusion of the solvent (14) from the dropletsinto the aqueous phase will cause the droplets to shrink. At equilibriumthe droplet will contain very little solvent and the result is a baseparticle comprising mostly cross-linked polyurea (15) throughout thethickness of the base particle and whatever other materials wereoriginally dissolved or dispersed in the solvent. For example, byintroducing a soluble dye or insoluble pigment in the solution ofwater-miscible solvent and water-dispersible polyfunctional isocyanates,a composite particle results having a base particle in which the dye orpigment is captured within a polyurea network formed afterpolymerization in the aqueous phase.

Therefore, the various methods for manufacturing a composite particleaccording to the present invention include first either dissolving a dyeand a water-dispersible polyfunctional isocyanate in a water-misciblesolvent or dispersing a pigment in a solution of the water-dispersiblepolyfunctional isocyanate and water-miscible solvent. The weight ratioof water-dispersible polyfunctional isocyanate to water-miscible solventis preferably 1:3 to 3:1, most preferably 1:2 to 2:1. The amount of dyeor pigment may be dependent on the desired opacity or transparency ofthe final composite particle.

In a second step, the mixture of dye/pigment, polyfunctional isocyanate,and water miscible solvent is added to an aqueous phase. Optionally,surfactants may be added to the aqueous phase and/or agitation rate maybe varied, for example, to control the final particle size.

As noted above, as water diffuses into the aqueous phase, thepolyfunctional isocyanates will cross-link via the previously describedhydrolysis reaction and amine condensation. The degree of cross-linkingwill be dependent on the temperature and on the time allowed forreaction to occur. Extending the length of time that the dyedsolution/pigment dispersion droplets are exposed to the aqueous phasewill increase the degree of cross-linking.

When a desired degree of cross-linking is achieved, the resultingcomposite particles containing the cross-linked polyurea network anddye/pigment may be separated from the aqueous phase (which contains thedissolved solvent). This may be achieved using any separation methodsknown by those of skill in the art including, but not limited to,filtration, centrifugation, drying, and combinations thereof. It ispreferred that most if not all of the water be removed from thecomposite for further processing, as will be described in greater detailbelow. Preferably the particles are separated from the aqueous phase bycentrifugation, after which they may be dried to remove residual waterand solvent.

Water-dispersible polyfunctional isocyanates that may be used to formthe composite particles according to the various embodiments of thepresent invention are known to those of skill in the art, such as thosesold under the tradename Bayhydur manufactured by Bayer Corporation. Thewater dispersible polyfunctional isocyanates preferably have an NCOcontent of about 5 to 35%, more preferably about 15-25%.

Water-miscible solvents that may be used in the methods for forming thecomposite particles according to the various embodiments of the presentinvention are preferably organic solvents in which the water-dispersiblepolyfunctional isocyanates are soluble. Such solvents are known to thoseof skill in the art and include, but are not limited to, tetrahydrofuran(THF), ketones and esters. The solvent should not contain nucleophilicgroups that might react with the isocyanates. One especially preferredwater-miscible solvent is methyl acetate. The preferred water solubilityof the water miscible solvent is at least 5%, more preferably at least25% by weight. The dyes and pigments that may be used in the compositeparticles according to the various embodiments of the present inventionare also known to those of skill in the art. The dyes are preferablysoluble in one or both of the water-dispersible polyfunctionalisocyanates and the water-miscible solvent. The dyes and pigments arealso preferably insoluble in water and insoluble in the non-polarsolvent of the electrophoretic medium in which the composite particleswill be added. Soluble dyes that may be incorporated in the compositeparticles according to the present invention include, but are notlimited to Solvent Blue 70, Solvent Blue 67, Solvent Blue 136, SolventRed 127, Solvent Red 130, Solvent Red 233, Solvent Red 125, Solvent Red122, Solvent Yellow 88, Solvent Yellow 146, Solvent Yellow 25, SolventYellow 89, Solvent Orange 11, Solvent Orange 99, Solvent Brown 42,Solvent Brown 43, Solvent Brown 44, Solvent Black 28, and Solvent Black29.

Pigments that are insoluble in the water-miscible solvents andwater-dispersible polyfunctional isocyanates may alternatively be usedin the methods to prepare the composite particles of the presentinvention. The pigments may be combined with the polyfunctionalisocyanate/solvent solutions to form a pigment dispersion and that aresubsequently introduced into the aqueous phase. Pigments that may beincorporated in the composite particles according to the presentinvention include, but are not limited to inorganic pigments, neatpigments, laked pigments, and organic pigments.

Examples of inorganic pigments include, but are not limited to, TiO₂,ZrO₂, ZnO, Al₂O₃, CI pigment black 26 or 28 or the like (e.g., manganeseferrite black spinel or copper chromite black spinel). Particles, suchas titania particles may be coated with a metal oxide, such as aluminumoxide or silicon oxide, for example.

Useful neat pigments include, but are not limited to, PbCrO₄, Cyan blueGT 55-3295 (American Cyanamid Company, Wayne, N.J.), Cibacron Black BG(Ciba Company, Inc., Newport, Del.), Cibacron Turquoise Blue G (Ciba),Cibalon Black BGL (Ciba), Orasol Black BRG (Ciba), Orasol Black RBL(Ciba), Acetamine Black, CBS (E. I. du Pont de Nemours and Company,Inc., Wilmington, Del., hereinafter abbreviated “du Pont”), CroceinScarlet N Ex (du Pont) (27290), Fiber Black VF (du Pont) (3023S), LuxolFast Black L (du Pont) (Solv. Black 17), Nirosine Base No. 424 (du Pont)(50415 B), Oil Black BG (du Pont) (Solv. Black 16), Rotalin Black RM (duPont), Sevron Brilliant Red 3 B (du Pont); Basic Black DSC (DyeSpecialties, Inc.), Hectolene Black (Dye Specialties, Inc.), AzosolBrilliant Blue B (GAF, Dyestuff and Chemical Division, Wayne, N.J.)(Solv. Blue 9), Azosol Brilliant Green BA (GAF) (Solv. Green 2), AzosolFast Brilliant Red B (GAF), Azosol Fast Orange RA Conc. (GAF) (Solv.Orange 20), Azosol Fast Yellow GRA Conc. (GAF) (13900 A), Basic BlackKMPA (GAF), Benzofix Black CW-CF (GAF) (35435), Cellitazol BNFV ExSoluble CF (GAF) (Disp. Black 9), Celliton Fast Blue AF Ex Conc (GAF)(Disp. Blue 9), Cyper Black IA (GAF) (Basic Black 3), Diamine Black CAPEx Conc (GAF) (30235), Diamond Black EAN Hi Con. CF (GAF) (15710),Diamond Black PBBA Ex (GAF) (16505); Direct Deep Black EA Ex CF (GAF)(30235), Hansa Yellow G (GAF) (11680); Indanthrene Black BBK Powd. (GAF)(59850), Indocarbon CLGS Conc. CF (GAF) (53295), Katigen Deep Black NNDHi Conc. CF (GAF) (15711), Rapidogen Black 3 G (GAF) (Azoic Black 4);Sulphone Cyanine Black BA-CF (GAF) (26370), Zambezi Black VD Ex Conc.(GAF) (30015); Rubanox Red CP-1495 (The Sherwin-Williams Company,Cleveland, Ohio) (15630); Raven 11 (Columbian Carbon Company, Atlanta,Ga.), (carbon black aggregates with a particle size of about 25 μm),Statex B-12 (Columbian Carbon Co.) (a furnace black of 33 μm averageparticle size), and chrome green.

Laked pigments are particles that have a dye precipitated on them orwhich are stained. Lakes are metal salts of readily soluble anionicdyes. These are dyes of azo, triphenylmethane or anthraquinone structurecontaining one or more sulphonic or carboxylic acid groupings. They areusually precipitated by a calcium, barium or aluminum salt onto asubstrate. Typical examples are peacock blue lake (Cl Pigment Blue 24)and Persian orange (lake of Cl Acid Orange 7), Black M Toner (GAF) (amixture of carbon black and black dye precipitated on a lake).

Organic pigment particles may include, but are not limited to, CIpigment PR 254, PR122, PR149, PG36, PG58, PG7, PB28, PB15:1, PB15:2,PB15:3, PB1:4, PY83, PY138, PY150, PY155 or PY20, as well as othercommonly used organic pigments described in color index handbooks, “NewPigment Application Technology” (CMC Publishing Co, Ltd, 1986) and“Printing Ink Technology” (CMC Publishing Co, Ltd, 1984). Specificexamples include Clariant Hostaperm Red D3G 70-EDS, Hostaperm PinkE-EDS, PV fast red D3G, Hostaperm red D3G 70, Hostaperm Blue B2G-EDS,Hostaperm Yellow H4G-EDS, Novoperm Yellow HR-70-EDS, Hostaperm GreenGNX, BASF Irgazine red L 3630, Cinquasia Red L 4100 HD, and Irgazin RedL 3660 HD; Sun Chemical phthalocyanine blue, phthalocyanine green,diarylide yellow or diarylide AAOT yellow.

The color provided by the dyes/pigments of the composite particlesaccording to the present invention may be white, black, red, green,blue, cyan, magenta, or yellow, for example. In addition to their color,the particles may have other distinct optical characteristics, such asoptical transmission, reflectance, luminescence, or, in the case ofdisplay media intended for machine reading, pseudo-color in the sense ofa change in reflectance of electromagnetic wavelengths outside thevisible range.

It is also noted that the composite particles may have differentparticle sizes. Useful sizes may range from 1 nm up to about 100 μm. Forexample, smaller particles may have a size which ranges from about 50 nmto about 800 nm. Larger particles may have a size which is about 2 toabout 50 times, and more preferably about 2 to about 10 times, the sizesof the smaller particles.

The composite particles made according to the various embodiments of thepresent invention may be further treated for surface modification. Suchsurface modification processes are known to those of skill in the art,like the processes disclosed in U.S. Patent Application No.2015/0218384, the contents of which are incorporated herein byreference.

For example, the stability of electrophoretic media may be improved byeither chemically bonding or cross-linking a steric stabilizing polymeraround the outside of the composite particle. The polymeric stabilizerdetermines the particle size and colloidal stability of the system andpreferably has a long polymeric chain which may stabilize the compositeparticles in a hydrocarbon solvent. The steric stabilizing polymer ispreferably from about 1 to about 15 percent by weight of the compositeparticle.

These polymer-coated composite particles may be prepared by a processcomprising (a) reacting the particle with a reagent having a functionalgroup capable of reacting with, and bonding to, the particle, and alsohaving a polymerizable or polymerization-initiating group, therebycausing the functional group to react with the particle surface andattach the polymerizable group thereto; and (b) reacting the product ofstep (a) with at least one monomer or oligomer under conditionseffective to cause reaction between the polymerizable orpolymerization-initiating group on the particle and the at least onemonomer or oligomer, thereby causing the formation of polymer bonded tothe particle.

Because the composite particles made according to the variousembodiments of the present invention will likely have available aminegroups on the surface of the particle, the available amine groups may bewith a reagent in a step (a) as described above having at least onefunctional group capable of reacting with the amine and at least onepolymerizable group. For example, the reagent for use in step (a) (theso-called “surface functionalization” step) of this process may includean isocyanate group and an acrylate group, such as isocyanate ethylacrylate. Alternatively, step (a) and (b) may be replaced with a singlestep by using a reagent that is already in polymeric form, if the stericstabilizing polymer includes a functional group, such as an isocyanategroup, that may react with the amine groups on the surface of thecomposite particle.

If a reagent, such as isocyanate ethyl acrylate, is used in a step (a),as described above, the polymeric stabilizer may be derived from one ormore monomers or macromonomers using various polymerization techniquesknown by those of skill in the art. For example, the polymericstabilizer may be obtained by random graft polymerization (RGP), ionicrandom graft polymerization (IRGP), and atom transfer radicalpolymerization (ATRP), as described in U.S. Pat. No. 6,822,782, thecontents of which are incorporated herein by reference in its entirety.As used herein throughout the specification and the claims,“macromonomer” means a macromolecule with one end-group that enables itto act as a monomer.

Suitable monomers for forming the polymeric stabilizer may include, butare not limited to, styrene, alpha methyl styrene, methyl acrylate,methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butylacrylate, t-butyl methacrylate, vinyl pyridine, N-vinylpyrrolidone,2-hydoxyethyl acrylate, 2-hydroxyethyl methacrylate, dimethylaminoethylmethacrylate, lauryl acrylate, lauryl methacrylate, 2-ethylhexylacrylate, 2-ethylhexyl methacrylate, hexyl acrylate, hexyl methacrylate,n-octyl acrylate, n-octyl methacrylate, n-octadecyl acrylate,n-octadecyl methacrylate, 2-perfluorobutylethyl acrylate,2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropylmethacrylate, 1,1,1,3,3,3-hexafluoroisopropyl acrylate,1,1,1,3,3,3-hexafluoroisopropyl methacrylate,2,2,3,3,3-pentafluoropropyl acrylate, 2,2,3,3-tetrafluoropropylacrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, and2,2,3,3,4,4,4-heptafluorobutyl methacrylate or the like. Themacromonomer may contain a terminal functional group selected from thegroup consisting of an acrylate group, a vinyl group, or combinationsthereof.

In describing the reagents used to provide the desired polymerizable orinitiating functionality, we do not exclude the possibility that thepolymeric stabilizer may be “bifunctional.” For example, polymerizationinitiators are known (such as 4,4′-azobis(4-cyanovaleric acid)) havingmore than one ionic site, and such initiators may be used in the presentprocess. Also, as previously noted, a bifunctional compound may have theform of a macromonomer containing repeating units having the capacity tobond to the particle surface and other repeated units having the desiredpolymerizable or initiating functionality, and such macromonomericbifunctional compounds may form polymeric stabilizers that will normallycontain multiple repeating units of both these types.

When choosing the bifunctional compound to provide polymerizable orinitiating functionality on the particle, attention should be paid tothe relative positions of the two groups within the reagent. As shouldbe apparent to those skilled in polymer manufacture, the rate ofreaction of a polymerizable or initiating group bonded to a particle mayvary greatly depending upon whether the group is held rigidly close tothe particle surface, or whether the group is spaced (on an atomicscale) from that surface and can thus extend into a reaction mediumsurrounding the particle, this being a much more favorable environmentfor chemical reaction of the group. In general, it is preferred thatthere be at least three atoms in the direct chain between the twofunctional groups.

In an alternative surface treatment method, the composite particles maybe treated by physi-sorption of a reagent comprising polymerizablegroups on to the surface of the composite particles by treating theparticle with a solution of a reagent having a polymerizable orpolymerization-initiating group, thereby causing the reagent to becomephysi-sorbed on to the particle surface such that the reagent will notdesorb from the particle surface when the particle is placed in ahydrocarbon medium. This process, as disclosed in U.S. PatentApplication No. 2015/0218384, may further comprise reacting thecomposite particle with the reagent physi-sorbed thereon with at leastone monomer or oligomer under conditions effective to polymerize thepolymerizable or polymerization-initiating group on the particle withthe at least one monomer or oligomer.

For example in one embodiment, the physi-sorption reagent may bedissolved in an ionic solvent or solvent mixture, such as awater/ethanol mixture. The process may include adjusting the pH of thesolution of the reagent to control the charge on the composite particle,and choosing the reagent to physi-sorb depending upon the desired chargeon the particle. As is well known to those skilled in pigment chemistry,the charge on many pigment particles in ionic liquids depends upon thepH of the liquid, there typically being one pH (the isoelectric point)at which the particle is uncharged. Above the isoelectric point of thepigment, the pigment is negatively charged and the reagent may contain aquaternary ammonium salt grouping (much in the way organo-clays areprepared), while below the isoelectric point, the positively chargedpigment surface can be modified by adsorption of reagents containinganionic functional groups. Reagents with quaternary ammonium saltgroupings include: [3-(methacryloyloxy)ethyl]trimethylammonium chloride(MAETAC), [3-(methacryloyloxy)ethyl]trimethylammonium methyl sulfate,and [3-(methacryloylamino)propyl]trimethylammonium chloride. Reagentswith anionic functional groups include 3-sulfopropyl methacrylatepotassium salt (SPMK) and sodium 4-vinylbenzenesulfonate. The process isnot restricted to pigments having inorganic oxide surfaces, and inprinciple may be extended to any pigments which can be chargedsufficiently to promote adsorption of the functionalizing reagent. Thereagent which is physi-sorbed on to the surface of the pigment particleshould desirably be chosen so that it becomes essentially irreversiblybound to the composite particle in the low dielectric constant solvents(typically aliphatic hydrocarbons) used in the polymerization step andin the internal phase of the final electrophoretic display.

In another surface treatment method, because amine groups on the surfaceof the composite particles are nucleophilic, the composite particles maybe treated with a reagent having a polymerizable orpolymerization-initiating group, and also comprising at least oneelectrophilic group. The electrophilic groups on the reagent react withthe nucleophilic groups on the particle surfaces, thus attaching thepolymerizable or polymerization-initiating groups to the particlesurface. This process may further comprise reacting the polymerizable orpolymerization-initiating groups with at least one of the monomers ormacromonomers previously described.

Electrophilic reagents useful in this process include acid halides, suchas 4-vinylbenzyl chloride and methacryloyl chloride, and2-isocyanatoethyl methacrylate. Both benzylic halides and acid chloridesare very reactive with respect to nucleophilic substitution reactions.For example, the coupling reaction with 4-vinylbenzyl chloride resultsin a styrene group tethered to the surface.

In a variation of the surface treatment described above using anelectrophilic reagent, the reagent may exclude a polymerizable orpolymerization-initiating group so that a residue of the reagent ischemically bonded to the pigment particle. The reagent may be chosen sothat the treatment of the composite particle therewith affects the zetapotential of the pigment particle. The preferred reagents for use inthis process are alkyl halides, especially benzyl chloride or bromide.Treatment with either benzyl chloride or bromide shifts the zetapotential of the pigment particle to more positive values.

In yet another surface treatment method, a silica coating may be appliedto the composite particle in a first step followed by a polymericcoating obtained by a dispersion polymerization technique, such as themethods described in U.S. Patent Application No. 20160085132, thecontents of which are incorporated herein by reference in its entirety.The polymeric coating will serve as a steric stabilizer of the compositeparticle in an electrophoretic medium, such as a non-polar solvent.

Various coating methods may be employed to provide the compositeparticle with a silica coating, for example, the coating methoddescribed in U.S. Pat. No. 3,639,133, the contents of which areincorporated herein by reference in its entirety. Prior to coating thecomposite particles, the particles may be prepared by firstde-agglomerating and homogenizing an aqueous slurry of the compositeparticles using methods such as sonication, ball milling, or jetmilling. A silica precursor may then be added to the aqueous slurry,such as sodium silicate or tetraethyl orthosilicate. In one process, thecomposite particles are dispersed in a solution of ethanol andtetraethyl orthosilicate and react at room temperature for 20 hrs underbasic conditions to form a generally uniform coating of silica over theparticles, wherein the silica content of the coated particles is about2% to 35% by weight.

After the deposition of the silica coating is complete, the pH of thereaction mixture may be reduced below about 4, and preferably to about3, before the silica-coated particles are separated from the reactionmixture. The reduction in pH is conveniently effected using sulfuricacid, although other acids, for example, nitric, hydrochloric andperchloric acids, may be used. The silica coated particles areconveniently separated from the reaction mixture by centrifugation.Following this separation, it is not necessary to dry the particles.Instead, the silica-coated particles can be readily re-dispersed in themedium, typically an aqueous alcoholic medium, to be used for the nextstep of the process for the formation of polymer on the particles. Thisenables the silica-coated particles to be maintained in anon-agglomerated and non-fused form as they are subjected to thedispersion polymerization processes for attachment of polymerizable orpolymerization-initiating groups, thus allowing for thorough coverage ofthe silica coated particle with such groups, and preventing theformation of large aggregates of particles.

During dispersion polymerization, monomer or a macromonomer containing aradically polymerizable group is polymerized around the silica coatedparticles in the presence of a bifunctional reagent. The solventselected as the reaction medium must be a good solvent for both themonomer or macromonomer and the bifunctional reagent, but a non-solventfor the polymer shell being formed. For example, in an aliphatichydrocarbon solvent of Isopar G®, monomer methylmethacrylate is soluble;but after polymerization, the resulting polymethylmethacrylate is notsoluble. The polymeric coating may be derived from various monomers andpolymerization techniques known by those of skill in the art, such asthose described above (e.g. random graft polymerization (RGP), ionicrandom graft polymerization (IRGP), and atom transfer radicalpolymerization (ATRP)).

The bifunctional reagent may be a reactive and polymerizablemacromonomer which adsorbs, becomes incorporated or is chemically bondedonto the surface of the silica shell and the polymeric coating. It willbe appreciated that because the silica coating completely covers thecomposite particles, any bifunctional reagent used to attach aninitiator or polymerizable group to the surface of the particle mustreact with the silica coating. The bifunctional reagent may also be anacrylate-terminated or vinyl-terminated macromolecule, which aresuitable because the acrylate or vinyl group can co-polymerize with themonomer in the reaction medium that will form the polymer shell. Themacromonomer preferably has a long hydrocarbon chain, which maystabilize the composite particles in a hydrocarbon solvent.

The preferred class of functional groups for bonding the bifunctionalreagents to silica-coated particles are silane coupling groups,especially trialkoxy silane coupling groups. One especially preferredreagent for attaching a polymerizable group to the silica coating is3-(trimethoxysilyl)propyl methacrylate, which is available commerciallyfrom Dow Chemical Company, Wilmington, Del. under the trade name Z6030.The corresponding acrylate may also be used.

One type of macromonomer for use as a steric stabilizer may be acrylateterminated polysiloxane, such as Gelest, MCR-M11, MCR-M17, or MCR-M22,for example. When choosing the bifunctional stabilizer to providepolymerizable or initiating functionality on the particle, attentionshould be paid to the relative positions of the two groups within thereagent. As should be apparent to those skilled in polymer manufacture,the rate of reaction of a polymerizable or initiating group bonded to aparticle may vary greatly depending upon whether the group is heldrigidly close to the particle surface, or whether the group is spaced(on an atomic scale) from that surface and can thus extend into areaction medium surrounding the particle, this being a much morefavorable environment for chemical reaction of the group. In general, itis preferred that there be at least three atoms in the direct chainbetween the two functional groups; for example,3-(trimethoxysilyl)propyl methacrylate provides a chain of four carbonand one oxygen atoms between the silyl and ethylenically unsaturatedgroups.

According to another embodiment of the present invention, the polymericshell on the silica coated organic pigment particles may be prepared byliving radical dispersion polymerization. The living radical dispersionpolymerization technique is similar to the dispersion polymerizationdescribed above by starting the process with silica coated compositeparticles and monomer and/or macromonomer dispersed in a reactionmedium. However in this alternative process, multiple living ends areformed on the surface of the shell. The living ends may be created byadding an agent such as TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy), aRAFT (reversible addition-fragmentation chain transfer) reagent or thelike, in the reaction medium, for the living radical polymerization.

A second monomer and/or macromonomer added to the reaction medium willreact with the living ends of the bifunctional reagent to form thepolymeric coating. The monomers may include any of the monomers orcomonomers previously listed.

In any of the processes described above, the quantities of the reagents,composite particles, monomer and/or macromonomers used may be adjustedand controlled to achieve the desired organic content in the resultingcomposite pigment particles. Furthermore, the processes of the presentinvention may include more than one stage and/or more than one type ofpolymerization.

As previously mentioned, the composite pigments of the present inventionmay be incorporated into electrophoretic media used for electro-opticdisplays. One or more of the composite particles may be dispersed in anencapsulated dispersion fluid, such as a dielectric solvent or solventmixture. The dispersion fluid may be encapsulated according to anymethod known to those of skill in the art, e.g. microcapsules,microcells, or a polymer matrix, and to any size or shape, such asspherical, for example, and may have diameters in the millimeter rangeor the micron range, but are preferably from about ten to about a fewhundred microns. The percentages of the composite particles in the fluidmay vary. For example, the particles may take up 0.1% to 50%, preferably0.5% to 15%, by volume of the electrophoretic fluid.

It is desirable that the polymeric stabilizer be highly compatible withthe encapsulated dispersion fluid. In practice, the suspending fluid inan electrophoretic medium is normally hydrocarbon-based and non-polar(e.g. C6-C18 branched alkanes), although the fluid can include aproportion of halocarbon, which is used to increase the density of thefluid and thus to decrease the difference between the density of thefluid and that of the particles. Accordingly, it is important that thepolymeric stabilizer formed in the present processes be highlycompatible with the encapsulated fluid, and thus that the polymericstabilizer itself comprise a major proportion of hydrocarbon chains;except for groups provided for charging purposes, as discussed below,large numbers of strongly ionic groups are undesirable since they renderthe polymeric stabilizer less soluble in the hydrocarbon suspendingfluid and thus adversely affect the stability of the particledispersion. Also, as already discussed, at least when the medium inwhich the particles are to be used comprises an aliphatic hydrocarbonsuspending fluid (as is commonly the case), it is advantageous for thepolymeric stabilizer to have a branched or “comb” structure, with a mainchain and a plurality of side chains extending away from the main chain.Each of these side chains should have at least about four, andpreferably at least about six, carbon atoms. Substantially longer sidechains may be advantageous; for example, some of the preferred polymericstabilizers may have lauryl (C₁₂) side chains. The side chains maythemselves be branched; for example, each side chain could be a branchedalkyl group, such as a 2-ethylhexyl group. It is believed (although theinvention is in no way limited by this belief) that, because of the highaffinity of hydrocarbon chains for the hydrocarbon-based suspendingfluid, the branches of the polymeric stabilizers spread out from oneanother in a brush or tree-like structure through a large volume ofliquid, thus increasing the affinity of the particle for the suspendingfluid and the stability of the particle dispersion.

There are two basic approaches to forming such a comb polymer. The firstapproach uses monomers which inherently provide the necessary sidechains. Typically, such a monomer has a single polymerizable group atone end of a long chain (at least four, and preferably at least six,carbon atoms). Monomers of this type which have been found to give goodresults in the present processes include hexyl acrylate, 2-ethylhexylacrylate and lauryl methacrylate. Isobutyl methacrylate and2,2,3,4,4,4-hexafluorobutyl acrylate have also been used successfully.In some cases, it may be desirable to limit the number of side chainsformed in such processes, and this can be achieved by using a mixture ofmonomers (for example, a mixture of lauryl methacrylate and methylmethacrylate) to form a random copolymer in which only some of therepeating units bear long side chains. In the second approach, typifiedby an RGP-ATRP process, a first polymerization reaction is carried outusing a mixture of monomers, at least one of these monomers bearing aninitiating group, thus producing a first polymer containing suchinitiating groups. The product of this first polymerization reaction isthen subjected to a second polymerization, typically under differentconditions from the first polymerization, so as to cause the initiatinggroups within the polymer to cause polymerization of additional monomeron to the original polymer, thereby forming the desired side chains. Aswith the bifunctional reagents discussed above, we do not exclude thepossibility that some chemical modification of the initiating groups maybe effected between the two polymerizations. In such a process, the sidechains themselves do not need to be heavily branched and can be formedfrom a small monomer, for example methyl methacrylate.

Free radical polymerization of ethylenic or similar radicalpolymerizable groups attached to particles may be effected at elevatedreaction temperatures, preferably 60 to 70 C, using conventional freeradical initiators, such as azobis(isobutyryinitrile) (AIBN), while ATRPpolymerization can be effected using the conventional metal complexes,as described in Wang, J. S., et al., Macromolecules 1995, 23, 7901, andJ. Am. Chem. Soc. 1995, 117, 5614, and in Beers, K. et al.,Macromolecules 1999, 32, 5772-5776. See also U.S. Pat. Nos. 5,763,548;5,789,487; 5,807,937; 5,945,491; 4,986,015; 6,069,205; 6,071,980;6,111,022; 6,121,371; 6,124,411; 6,137,012; 6,153,705; 6,162,882;6,191,225; and 6,197,883. The entire disclosures of these papers andpatents are herein incorporated by reference. The presently preferredcatalyst for carrying out ATRP is cuprous chloride in the presence ofbipyridyl (Bpy).

RGP processes of the invention in which particles bearing polymerizablegroups are reacted with a monomer in the presence of an initiator willinevitably cause some formation of “free” polymer not attached to aparticle, as the monomer in the reaction mixture is polymerized. Theunattached polymer may be removed by repeated washings of the particleswith a solvent (typically a hydrocarbon) in which the unattached polymeris soluble, or (at least in the case of metal oxide or other denseparticles) by centrifuging off the treated particles from the reactionmixture (with or without the previous addition of a solvent or diluent),redispersing the particles in fresh solvent, and repeating these stepsuntil the proportion of unattached polymer has been reduced to anacceptable level. (The decline in the proportion of unattached polymercan be followed by thermogravimetric analysis of samples of thepolymer.) Empirically, it does not appear that the presence of a smallproportion of unattached polymer, of the order of 1 percent by weight,has any serious deleterious effect on the electrophoretic properties ofthe treated particles; indeed, in some cases, depending upon thechemical natures of the unattached polymer and the suspending fluid, itmay not be necessary to separate the particles having attached polymericstabilizers from the unattached polymer before using the particles in anelectrophoretic display.

As already indicated, it has been found that there is an optimum rangefor the amount of polymeric stabilizer which should be formed onelectrophoretic particles, and that forming an excessive amount ofpolymer on the particles can degrade their electrophoreticcharacteristics. The optimum range will vary with a number of factors,including the density and size of the particles being coated, the natureof the suspending medium in which the particles are intended to be used,and the nature of polymer formed on the particles, and for any specificparticle, polymer and suspending medium, the optimum range is bestdetermined empirically. However, by way of general guidance, it shouldbe noted that the denser the particle, the lower the optimum proportionof polymer by weight of the particle, and the more finely divided theparticle, the higher the optimum proportion of polymer. In general, theparticles should be coated with at least about 2, and desirably at leastabout 4, percent by weight of the particle. In most cases, the optimumproportion of polymer will range from about 4 to about 15 percent byweight of the particle, and typically is about 6 to about 15 percent byweight, and most desirably about 8 to about 12 percent by weight.

To incorporate functional groups for charge generation of the pigmentparticles, a co-monomer may be added to the polymerization reactionmedium. The co-monomer may either directly charge the composite pigmentparticles or have interaction with a charge control agent in the displayfluid to bring a desired charge polarity and charge density to thecomposite pigment particles. Suitable co-monomers may include acrylicacid, methacrylic acid, vinyl phosphoric acid,2-acrylamino-2-methylpropane sulfonic acid, 2-(dimethyl amino)ethylmethacrylate, N-[3-(dimethylamino)propyl]methacrylamide and the like.Suitable co-monomers may also include fluorinated acrylate ormethacrylate such as 2-perfluorobutylethyl acrylate, 2,2,2trifluoroethyl methacrylate, 2,2,3,3 tetrafluoropropyl methacrylate,1,1,1,3,3,3-hexafluoroisopropyl acrylate,1,1,1,3,3,3-hexafluoroisopropyl methacrylate,2,2,3,3,3-pentafluoropropyl acrylate, 2,2,3,3-tetrafluoropropylacrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate or2,2,3,3,4,4,4-heptafluorobutyl methacrylate. Alternatively, charged orchargeable groups may be incorporated into the polymer via thebifunctional stabilizer used to provide polymerizable or initiatingfunctionality to the pigment.

Functional groups, such as acidic or basic groups, may be provided in a“blocked” form during polymerization, and may then be de-blocked afterformation of the polymer. For example, since ATRP cannot be initiated inthe presence of acid, if it is desired to provide acidic groups withinthe polymer, esters such as t-butyl acrylate or isobornyl methacrylatemay be used, and the residues of these monomers within the final polymerhydrolyzed to provide acrylic or methacrylic acid residues.

When it is desired to produce charged or chargeable groups on thecomposite particles and also polymeric stabilizers separately attachedto the particles, it may be very convenient to treat the particles witha mixture of two reagents, one of which carries the charged orchargeable group (or a group which will eventually be treated to producethe desired charged or chargeable group), and the other of which carriesthe polymerizable or polymerization-initiating group. Desirably, the tworeagents have the same, or essentially the same, functional group whichreacts with the particle surface so that, if minor variations inreaction conditions occur, the relative rates at which the reagentsreact with the particles will change in a similar manner, and the ratiobetween the number of charged or chargeable groups and the number ofpolymerizable or polymerization-initiating groups will remainsubstantially constant. It will be appreciated that this ratio can bevaried and controlled by varying the relative molar amounts of the two(or more) reagents used in the mixture.

The density of the electrophoretic particle may be substantially matchedto that of the suspending (i.e., electrophoretic) fluid. As definedherein, a suspending fluid has a density that is “substantially matched”to the density of the particle if the difference in their respectivedensities is between about zero and about two grams/milliliter (“g/ml”).This difference is preferably between about zero and about 0.5 g/ml.

The solvent in which the composite particles are dispersed may be clearand colorless. It preferably has a low viscosity and a dielectricconstant in the range of about 2 to about 30, preferably about 2 toabout 15 for high particle mobility. Examples of suitable dielectricsolvent include hydrocarbons such as isopar, decahydronaphthalene(DECALIN), 5-ethylidene-2-norbornene, fatty oils, paraffin oil, siliconfluids, aromatic hydrocarbons such as toluene, xylene,phenylxylylethane, dodecylbenzene or alkylnaphthalene, halogenatedsolvents such as perfluorodecalin, perfluorotoluene, perfluoroxylene,dichlorobenzotrifluoride, 3,4,5-trichlorobenzotrifluoride,chloropentafluorobenzene, dichlorononane or pentachlorobenzene, andperfluorinated solvents such as FC-43, FC-70 or FC-5060 from 3M Company,St. Paul Minn., low molecular weight halogen containing polymers such aspoly(perfluoropropylene oxide) from TCI America, Portland, Oreg.,poly(chlorotrifluoroethylene) such as Halocarbon Oils from HalocarbonProduct Corp., River Edge, N.J., perfluoropolyalkylether such as Galdenfrom Ausimont or Krytox Oils and Greases K-Fluid Series from DuPont,Del., polydimethylsiloxane based silicone oil from Dow-Corning (DC-200).

Charge control agents may be used, with or without charged groups inpolymer coatings, to provide good electrophoretic mobility to theelectrophoretic particles. Stabilizers may be used to preventagglomeration of the electrophoretic particles, as well as prevent theelectrophoretic particles from irreversibly depositing onto the capsulewall. Either component can be constructed from materials across a widerange of molecular weights (low molecular weight, oligomeric, orpolymeric), and may be a single pure compound or a mixture. The chargecontrol agent used to modify and/or stabilize the particle surfacecharge is applied as generally known in the arts of liquid toners,electrophoretic displays, non-aqueous paint dispersions, and engine-oiladditives. In all of these arts, charging species may be added tonon-aqueous media in order to increase electrophoretic mobility orincrease electrostatic stabilization. The materials can improve stericstabilization as well. Different theories of charging are postulated,including selective ion adsorption, proton transfer, and contactelectrification.

An optional charge control agent or charge director may be incorporatedin the electrophoretic fluid. These constituents typically consist oflow molecular weight surfactants, polymeric agents, or blends of one ormore components and serve to stabilize or otherwise modify the signand/or magnitude of the charge on the electrophoretic particles.Additional pigment properties which may be relevant are the particlesize distribution, the chemical composition, and the lightfastness.

Charge adjuvants may also be added. These materials increase theeffectiveness of the charge control agents or charge directors. Thecharge adjuvant may be a polyhydroxy compound or an aminoalcoholcompound, and is preferably soluble in the suspending fluid in an amountof at least 2% by weight. Examples of polyhydroxy compounds whichcontain at least two hydroxyl groups include, but are not limited to,ethylene glycol, 2,4,7,9-tetramethyldecyne-4,7-diol, polypropyleneglycol), pentaethylene glycol, tripropylene glycol, triethylene glycol,glycerol, pentaerythritol, glycerol tris(12-hydroxystearate), propyleneglycerol monohydroxystearate, and ethylene glycol monohydroxystearate.Examples of aminoalcohol compounds which contain at least one alcoholfunction and one amine function in the same molecule include, but arenot limited to, triisopropanolamine, triethanolamine, ethanolamine,3-amino-1-propanol, o-aminophenol, 5-amino-1-pentanol, andtetrakis(2-hydroxyethyl)ethylenediamine. The charge adjuvant ispreferably present in the suspending fluid in an amount of about 1 toabout 100 milligrams per gram (“mg/g”) of the particle mass, and morepreferably about 50 to about 200 mg/g.

In general, it is believed that charging results as an acid-basereaction between some moiety present in the continuous phase and theparticle surface. Thus useful materials are those which are capable ofparticipating in such a reaction, or any other charging reaction asknown in the art.

Different non-limiting classes of charge control agents which are usefulinclude organic sulfates or sulfonates, metal soaps, block or combcopolymers, organic amides, organic zwitterions, and organic phosphatesand phosphonates. Useful organic sulfates and sulfonates include, butare not limited to, sodium bis(2-ethylhexyl) sulfosuccinate, calciumdodecylbenzenesulfonate, calcium petroleum sulfonate, neutral or basicbarium dinonylnaphthalene sulfonate, neutral or basic calciumdinonylnaphthalene sulfonate, dodecylbenzenesulfonic acid sodium salt,and ammonium lauryl sulfate. Useful metal soaps include, but are notlimited to, basic or neutral barium petronate, calcium petronate, Co—,Ca—, Cu—, Mn—, Ni—, Zn—, and Fe— salts of naphthenic acid, Ba—, Al—,Zn—, Cu—, Pb—, and Fe— salts of stearic acid, divalent and trivalentmetal carboxylates, such as aluminum tristearate, aluminum octanoate,lithium heptanoate, iron stearate, iron distearate, barium stearate,chromium stearate, magnesium octanoate, calcium stearate, ironnaphthenate, zinc naphthenate, Mn— and Zn— heptanoate, and Ba—, Al—,Co—, Mn—, and Zn— octanoate. Useful block or comb copolymers include,but are not limited to, AB diblock copolymers of (A) polymers of2-(N,N-dimethylamino)ethyl methacrylate quaternized with methylp-toluenesulfonate and (B) poly(2-ethylhexyl methacrylate), and combgraft copolymers with oil soluble tails of poly(12-hydroxystearic acid)and having a molecular weight of about 1800, pendant on an oil-solubleanchor group of poly(methyl methacrylate-methacrylic acid). Usefulorganic amides include, but are not limited to, polyisobutylenesuccinimides such as OLOA 371 or 1200 (available from Chevron OroniteCompany LLC, Houston, Tex.), or Solsperse 19000 and Solsperse 17000(available from Avecia Ltd., Blackley, Manchester, United Kingdom;“Solsperse” is a Registered Trade Mark), and N-vinylpyrrolidonepolymers. Useful organic zwitterions include, but are not limited to,lecithin. Useful organic phosphates and phosphonates include, but arenot limited to, the sodium salts of phosphated mono- and di-glycerideswith saturated and unsaturated acid substituents.

Particle dispersion stabilizers may be added to prevent particleflocculation or attachment to the capsule walls. For the typical highresistivity liquids used as suspending fluids in electrophoreticdisplays, non-aqueous surfactants may be used. These include, but arenot limited to, glycol ethers, acetylenic glycols, alkanolamides,sorbitol derivatives, alkyl amines, quaternary amines, imidazolines,dialkyl oxides, and sulfosuccinates.

If a bistable electrophoretic medium is desired, it may be desirable toinclude in the suspending fluid a polymer having a number averagemolecular weight in excess of about 20,000, this polymer beingessentially non-absorbing on the electrophoretic particles;poly(isobutylene) is a preferred polymer for this purpose. See U.S. Pat.No. 7,170,670, the entire disclosure of which is herein incorporated byreference.

EXAMPLES

The following examples are given as illustrative embodiments of thepresent invention, and are not intended to limit the scope of theinvention.

Step 1:

Sample 1

Approximately 2 g of Solvent Blue 70 was dissolved in a solution of 10 gof Bayhydur 302 and 10 g tetrahydrofuran (THF) at room temperature(approximately 20° C.). The solution was then added subsurface by meansof a pipette to a stirred flask containing deionized water (100 g) at25° C. The mixture so formed was stirred overnight and then centrifuged(at 3500 rpm for 30 minutes) followed by decantation of the supernatantliquid. The cake of dyed particles that resulted was air dried, thenbroken up with a spatula.

Sample 2

The same process as Example 1 was repeated except that 2 g of OrasolYellow GLN was used in place of the Solvent Blue 70.

Step 2:

4.5 g of Samples 1 and 2 were each separately combined with Isopar-E (18g) and a Solsperse 17k (4.5 g of a 20% solution in isopar-E) in a glassjar containing a magnetic stirring bar. Glass beads of 3 mm diameter (20g) were added and the mixture was stirred overnight to provide a slurryof small dyed particles.

Analysis by microscopy of the slurries revealed particles ranging insize from about 0.5-5 microns.

While preferred embodiments of the invention have been shown anddescribed herein, it will be understood that such embodiments areprovided by way of example only. Numerous variations, changes, andsubstitutions will occur to those skilled in the art without departingfrom the spirit of the invention. Accordingly, it is intended that theappended claims cover all such variations as fall within the spirit andscope of the invention.

We claim:
 1. A method of making a composite particle comprising thesteps: mixing a dye or a pigment with a water-dispersible polyfunctionalisocyanate in a water-miscible solvent to form a dye solution or apigment dispersion, the water-dispersible polyfunctional isocyanatecomprising a hydrophilic oligomeric group, wherein the hydrophilicoligomeric group comprises polyethylene oxide, and at least oneisocyanate group; adding the dye solution or the pigment dispersion toan aqueous phase to form an emulsion; agitating the emulsion while thepolyfunctional isocyanate is converted into a cross-linked polyurea byhydrolyzing isocyanate groups towards amine groups that react withunhydrolyzed isocyanate groups; and separating the composite particlescontaining the cross-linked polyurea and the dye or pigment from theemulsion.
 2. The method of claim 1, wherein the cross-linked polyurea isformed by a monomer or oligomer of water-dispersible polyfunctionalisocyanate.
 3. The method of claim 1, wherein the water-dispersiblepolyfunctional isocyanate has NCO content of about 5 to 35%.
 4. Themethod of claim 1, wherein the cross-linked polyurea of the compositeparticles comprises amine groups.
 5. The method of claim 4, furthercomprising a step of forming a stabilizing polymer on the surface of thecomposite particle, the stabilizing polymer being covalently bonded tothe cross-linked polyurea.
 6. The method of claim 5, wherein the step offorming the stabilizing polymer comprises (a) reacting an amine group ofthe cross-linked polyurea with a first reagent, the first reagentcomprising a first functional group capable of reacting with the aminegroup of the cross-linked polyurea and a second polymerizable functionalgroup, and (b) reacting the product of step (a) with a second monomer oroligomer under conditions effective to cause reaction between the secondpolymerizable functional group and the second monomer or oligomer. 7.The method of claim 6, wherein the first functional group of the firstreagent is an electrophilic group.
 8. The method of claim 6, wherein thesecond polymerizable functional group of the first reagent is anacrylate functional group, a methacrylate functional group or a vinylfunctional group.
 9. The method of claim 5, wherein the step of formingthe stabilizing polymer comprises (a) reacting an amine group of thecross-linked polyurea with a second reagent, the second reagentcomprising a first functional group capable of reacting with the aminegroup of the cross-linked polyurea and a third polymerization initiationfunctional group, and (b) reacting the product of step (a) with a thirdmonomer or oligomer under conditions effective to cause reaction betweenthe third polymerization initiating functional group and the thirdmonomer or oligomer.
 10. The method of claim 9, wherein the thirdpolymerizable functional group of the second reagent is an acrylatefunctional group, a methacrylate functional group or a vinyl functionalgroup.
 11. The method of claim 1, wherein the hydrophilic oligomericgroup is aliphatic.
 12. The method of claim 1, wherein thewater-miscible solvent has a water solubility of at least 25% by weight.13. The method of claim 1, wherein the dye is insoluble in water andsoluble in the water-miscible solvent.
 14. The method of claim 13,wherein the dye is selected from the group consisting of Solvent Blue70, Solvent Blue 67, Solvent Blue 136, Solvent Red 127, Solvent Red 130,Solvent Red 233, Solvent Red 125, Solvent Red 122, Solvent Yellow 88,Solvent Yellow 146, Solvent Yellow 25, Solvent Yellow 89, Solvent Orange11, Solvent Orange 99, Solvent Brown 42, Solvent Brown 43, Solvent Brown44, Solvent Black 28, Solvent Black 29, and combinations thereof. 15.The method of claim 1, further comprising a step of forming astabilizing polymer on the surface of the composite particle, thestabilizing polymer being physi-sorbed to the cross-linked polyurea. 16.The method of claim 15, wherein the steric stabilizing polymer is formedvia dispersion polymerization.
 17. The method of claim 16, wherein thesteric stabilizing polymer is formed via living radical dispersionpolymerization.
 18. The method of claim 15, wherein the stabilizingpolymer is formed by treating the cross-linked polyurea with a solutionhaving a fourth monomer or oligomer under conditions effective topolymerize the fourth monomer or oligomer.
 19. The method of claim 15,wherein the composite particle is formed by (a) coating the cross-linkedpolyurea with silica, (b) treating the silica coated particle with athird reagent comprising a silane coupling group and a fourthpolymerizable functional group, and (c) treating the product of step (b)with a fifth monomer or oligomer to cause reaction between the fourthpolymerizable functional group and the fifth monomer or oligomer.